JPS58141238A - Polyester composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled compsn. having excellent electrostatic castability during the molding thereof into a film, by reacting a dissolved lithium compd. with a phosphorus compd. during the course of the polymn. reaction of a polyester to precipitate insoluble particles, and then adding a magnesium compd. soluble in the polyester thereto. CONSTITUTION:A lithium compd. such as lithium acetate and/or a calcium compd. such as calcium acetate is/are dissolved in a reaction medium. An acid component such as terephthalic acid is reacted with an alcohol component such as ethylene glycol in said reaction medium. Before a polycondensation reaction is completed, a phosphorus compd. such as phosphoric acid is added thereto to precipitate particles contg. phosphorus and lithium and/or calcium. Then a magnesium compd. and/or a manganese compd. soluble in a polyester, such as magnesium acetate tetrahydrate and/or managanese acetate tetrahydrate, is/are added thereto. The reaction is continued to produce a polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyester compositions and methods of making the same.

For more details on the east, the electrostatic application castability during film formation has been revised,
The present invention also relates to a polyester composition having excellent slip properties and a method for producing the same. Biaxially oriented films of polyester, especially polyethylene terephthalate, have excellent mechanical properties, electrical properties, chemical resistance, dimensional stability, etc. Therefore, polyester film is used as a base material in many fields such as magnetic tape, capacitors, packaging, plate making, electrical disconnection, and photographic film, and its required properties differ depending on each use. However, the universally desired characteristic is excellent workability when handling the film, that is, a low coefficient of friction of the film.

One practical method for improving the slipperiness of polyester films is to add inert inorganic compound fine particles to polyester, but particle classification and dispersion operations are complicated, and there are problems with the contamination of coarse particles. This is unavoidable, and it is difficult to apply it to high-grade films such as magnetic tape and capacitor films, for which demand has increased rapidly in recent years.

Another method is the so-called precipitation method, which uses the residual metal compound in polyester to precipitate fine particles. If it is possible to adopt the rounding and precipitation method, which has the advantage that it can be applied easily, its utility value is extremely large.

Of course, using this precipitation method, not all of the nine polyesters have a high degree of slipperiness, and among them, seven or more alkali metal compounds and alkaline earth metal compounds are combined with phosphorus compounds, especially plated metal compounds. React with phosphorus compounds in an amount greater than the total amount, phosphoric acid or sulfuric acid derivative O
It is known that a method of precipitation as metal salt particles is preferred.

In the absence of phosphorus compounds, these metal compounds precipitate as metal salts in polyester oligomers, but these are not compatible with polyester, are easily destroyed by stretching, and have little effect on improving slipperiness. . As the ratio of the phosphorus compound added to the metal compound increases, the affinity with the polyester is improved, and this improvement effect becomes particularly pronounced when a small amount or more of the phosphorus compound is coexisting.

By the way, in recent years, the requirements for film quality have become increasingly strict, and in particular, reducing long-term waviness of the film, that is, improving thickness accuracy, has become an essential condition.

In this tank, for example, 1% of the sheet material is melted and extruded from the extrusion die, as shown in the publication No. A so-called electrostatic application cooling method is known in which a cough sheet-like material is brought into close contact with a cooling surface by applying an electrostatic charge.

However, in this electrostatic application cooling method, when the speed of the rotating cooling drum is increased for the purpose of increasing productivity, the contact force between the sheet material and the cooling drum decreases, and so-called bound bubbles are generated. This is unacceptable as a quality characteristic required for the product.

These bound bubbles are generally more likely to occur when the raw material polyester has a high resistivity #1 when melted, and when the value measured by the method described below exceeds 1 x 10"Ω, making it possible to efficiently produce a high-quality film. However, according to the knowledge of the present inventors, polyester containing particles mainly composed of a metal salt of a phosphorus compound that provides excellent lubricity usually has a specific resistance when melted of J X /
Rounding exceeding 0@Ω-country has the disadvantage that this electrostatic application cooling method cannot be effectively applied.

One known method for lowering the specific resistance of polyester during melting is to add a metal compound such as magnesium or manganese during polyester production. It has the disadvantage that it cannot be changed independently.

A method of diluting a polyester containing nine precipitated particles with a polyester that does not contain particles and has a low resistivity when melted in a bath is also considered, but in this case as well, the particle-antinand 1w1iii! The disadvantage is that the resistivity cannot be independently controlled.

In view of the above-mentioned circumstances, the inventors of the present invention have determined that when producing a polyester containing particles mainly composed of metal salts of metal phosphides, the precipitated particles and the region where no precipitated particles exist, that is, the polyester matrix, are separated. We came up with the idea of controlling this and completed the present invention.

That is, in the present invention, precipitated particles containing lithium and/or calcium and phosphorus elements are mixed at a rate of 0.0/~/wt.
and a polyester composition containing o, or to 1 mol of a magnesium compound and/or manganese compound soluble in the polyester as a metal element based on all the components of the polyester, and a polyester composition containing terephthalic acid or a lower alkyl ester thereof as the main acid. In the method for producing polyester having a glycol component mainly composed of ethylene glycol, on the R floor before the polycondensation reaction is completed,
By the reaction between the lithium compound and the calcium compound which are substantially dissolved in the reaction system and the phosphorus compound, the lithium and the calcium compound produce particles containing calcium and phosphorus elements, and then the magnesium compound and the calcium compound are reacted with the phosphorus compound. This invention relates to a method for producing polyester characterized by adding a manganese compound.

The present invention will be explained in more detail below. In the present invention, the polyester refers to a polyester having ethylene terephthalate as a main component. Specifically, terephthalate is the acid component that produces its lower alkyl ester, and ethylene glycol; - There are many things that can be obtained as glycol components that produce alcohol. Of course, some of these raw materials may be replaced with other acid components or glycol components, but in any case, the term "polyester" as used in the present invention refers to a polyester in which 10 moles or more of ``fumed tylene terephthalate units'' are used. .

The greatest feature of the present invention is that the precipitated particles and the polyester matrix are independently controlled. In this case, the precipitated particles refer to particles generated within the reaction system at any time during the polyester manufacturing process, and the specific Specifically, it refers to particles produced by a reaction between at least one compound selected from lithium compounds or calcium compounds and a phosphorus compound in an amount of approximately one or more equivalents, preferably at least o, r equivalent to the excipient compound.

As for lithium "119" which can be suitably used, calcium compounds include oxides, chlorides, hydrides, carbonates, carboxylates, and alcoholades, with lithium acetate or calcium acetate being particularly preferred.As a phosphorus compound, For example, phosphoric acid, phosphorous acid, trialkyl esters or partial alkyl esters thereof, etc. can be used.

Examples of precipitated particles suitable for use in the present invention include: ■ Precipitated particles containing lithium and phosphorus elements; ■ Precipitated particles containing calcium and phosphorus elements; ■ Precipitated particles containing lithium, calcium, and phosphorus base.・In addition, in the present invention, these precipitated particles have a membership fee of 0.0/~/, 0@amount-contained relative to the polyester. If the amount of precipitated particles is too small, the lubricity of the polyester film will not be improved, and if it is too large, coarse particles or agglomerated particles will occur frequently, making it impossible to obtain a high-quality film.

It is preferable that calcium and phosphorus elements are contained in the Libram 119 in an amount of 1 weight or more for each precipitated particle. Among these precipitated particles, those having a composition in which the phosphorus element contained therein has a tl of 1 or more, preferably 0.1 or more weight relative to the lithium or calcium element have excellent affinity for polyester. Therefore, it is suitable for use in the present invention.

A specific example of producing precipitated particles suitable for K used in the present invention is as follows.

(2) The esterified or transesterified product (hereinafter referred to as polyester oligomer) K lithium compound is present in a dissolved state, and KtR is added with an equivalent or more of a phosphorus compound mainly consisting of trialkyl phosphate.

■ A calcium compound is present in a dissolved state in the polyester oligomer, and a phosphorus compound mainly consisting of trialkyl phosphate and trialkyl phosphite is added so that the total amount of phosphorus compound is approximately equivalent or more to the calcified metal. .

(2) A lithium compound and a calcium compound are present in a dissolved state in a polyester oligomer, and an approximately equivalent amount or more of a phosphorus compound mainly composed of trialkyl phosphate is added thereto.

In these cases, it is of course possible to add part or all of the lithium compound or calcium compound in advance during the esterification or transesterification reaction, and if necessary, the operation of adding the lithium compound or calcium compound after the esterification or transesterification reaction may be added. You can also add it.

In any case, it is necessary that these lithium and calcium compounds are substantially dissolved in the polyester oligomer at the time of adding the phosphorus compound.

The amount of calcified metal in the lithium compound i9 used is 0.0% relative to the total amount constituting the polyester. Oj-
/7%, preferably, the resistance is not improved at all, and when used in excess of %*/%, coarse particles or aggregated particles frequently occur, so the value as a film. becomes impaired.

It is preferable to use the phosphorus compound in an elemental amount of approximately equivalent or more, specifically, o, r equivalent or more, with respect to lithium or the calcified metal. This is because in this case most or all of the precipitated particles C)11 are obtained as particles of the lithium or calcium salt of the phosphoric acid or phosphorous #spun. Since these precipitated particles have excellent filler properties with polyester, they are hardly destroyed during stretching and work extremely effectively in improving the slipperiness of the film.

The equivalent ratio of phosphorus element to lithium or calcium is expressed by the following formula (where P, M and MB are the numbers of cells of phosphorus, lithium and calcium elements in the phosphorus compound, lithium compound and calcium compound, respectively). ).

In the present invention, K is used in this way to obtain precipitated particles that are effective in improving the film's adhesion properties, but in the polyester containing these particles, the curved portion or almost all of the lithium compound or calcium compound is Since the lithium or calcium compounds are precipitated as salts of phosphorus compounds, the amount of dissolved lithium or calcium compounds present in the polyester is extremely small.Therefore, the specific resistance of the phosphorus polyester when melted is high, that is, usually 5xio''Ω- It becomes difficult to effectively apply the rounding electrostatic application cooling method exceeding α.

As a result of intensive studies to solve this problem, the inventor of the present invention found that while the precipitated particles are present, a metal compound soluble in polyester is made to exist in a dissolved state in a region that does not contain precipitated particles, that is, in the polyester matrix. This is an innovative method that has been developed.

Here, the metal compound soluble in polyester refers to a compound of magnesium 19 and manganese, but these metal compounds that can be used in the present invention include oxides, chlorides, hydrides, carbonates, and carboxylic acids. Salt, alcoholado, etc. can be mentioned. (Hereinafter, simply speaking of a metal element or a metal compound, magnesium refers to the element manganese or a compound thereof.) The amount of these metal compounds used is preferably 0.0 to 1 mole based on the total amount of components constituting the polyester. is 0. /
Selected from the range -0.4 mol-○. If this amount is more than 1 mol, the thermal stability of the polyester will be impaired, and even if it is less than O1θr mol, it will not be effective in lowering the specific resistance value of the polyester.

The amount of these metal compounds used to obtain the precipitated particles depends on the amount of nine lithium compounds or calcium compounds and phosphorus compounds, but is determined by the following formula (where P, MA, and MB are in the case of formula (1)). It is synonymous and 1
MO indicates the number of moles of the metal element in the magnesium or manganese compound. ) is preferably added so as to satisfy the following. (The above MA,
MB and MO are collectively referred to as all-metallic elements, and their compounds are referred to as all-metallic compounds. ) The equivalent ratio of phosphorus element to all metal elements contained in the reaction system is 7.
When the resistivity exceeds rxio”Ω, the resistivity during melting is often
- If the value is less than 0.2, diethylene glycol bonds are likely to form in the polyester, resulting in poor thermal stability. At the same time, the color tone also became unattractive.
Become.

For lithium compounds, when the amount of calcified metal and phosphorus compound is constant, increase the amount of metal compound added #1
It is more preferable that the specific resistance value is smaller.

Next, this is the third aspect of the present invention, but the inventor of the present invention first [clarified] that these metal compounds must be added after the formation of precipitated particles is substantially completed. According to Toro K, these precipitated particles undergo a process of generation, growth, and ripening, but when they come into contact with an iron metal compound during the nucleation or growth stage, they take on a completely different form than originally intended. That is, in many cases it becomes solubilized,
It has been found that even if the precipitated particles are once aged in polyester oligo i- and then brought into contact with the metal compound, there is almost no reaction between the two.

Therefore, according to the method of the present invention, the wrinkled metal compound can be dispersed and dissolved in the polyester matrix without substantially changing the particle size and particle amount of the precipitated particles. In other words, the method of the present invention can improve particle morphology and fs for the first time.
It is possible to change the resistivity at 11 and 11 independently.

The degree of ripening of the precipitated particles varies depending on the type of particles, the composition of the polyester oligomer, the temperature, etc., so it cannot be determined uniquely, but usually a phosphorus compound is added to a thread containing a lithium compound or a calcium compound. It takes 1.20 to 100 minutes. In this case, if the reaction system is maintained at a high temperature or the average degree of polymerization of the polyester oligomer is increased, the heating time Fi can be shortened.

In the present invention, polyester is produced by adding a metal compound and then carrying out a polycondensation reaction. In this case, conventionally known polycondensed gold catalysts such as antimony compounds, germanium compounds, etc. can be used. This heavy condensed gold catalyst is not included in the calculation of the equivalence ratio between the phosphorus compound and the metal compound.

The polycondensation catalyst may be added to the reaction system before adding the metallized metal, if necessary, but it is also preferable to add it after the phosphorus compound is added.

As mentioned above, the present invention has a particularly effective effect on improving the slipperiness of polyester films. It has the characteristics of being able to maintain the film surface condition while improving the electrostatic application castability.

Hereinafter, the present invention will be explained by way of examples.
However, the present invention is not limited to the following embodiments as long as they do not exceed the gist thereof. In Examples and Comparative Examples, "1 part" indicates "parts by weight."

The Aya-ashi method used is shown below.

(1) Measurement of amount of precipitated particles Polyester 10011 (J-chlorophenol/,
OL is added and heated at 120°C for 3 hours, centrifuged at 0,000 rpm for a0 minutes using an ultracentrifuge LJ-30 manufactured by Tomago Peckman, and the resulting particles are vacuum-dried at 100°C. When the particles were measured with a scanning differential calorimetry needle, poly!
If a melting peak corresponding to - is introduced, O-chlorophenol is added to the particles, heated and cooled, and centrifuged again. Specially sold particles whose melting peak is no longer observed are defined as precipitated particles. Normally, one centrifugation operation is sufficient.

<2) Add #liquid haze polyester 1, 7 # to a mixed solution λO- of keto 2 chloro/phenol/phenol in a ratio of 2/6 (weight ratio), and add approximately
After heating and dissolving at 0°C for 1 hour, the solution was cooled, a portion of the solution was collected into a 10 mm thick quartz glass cell, and measured using an integrating sphere hazemeter (Nippon Seimitsu Optics mHBR type) at the light source wavelength.
Measured in Onm.

In general, this value increases as the particle diameter of the particles contained in the polyester increases and the amount of particles contained in the polyester increases.

(3) Measurement of resistivity during melting of polyester using British National Op Applied Physics (NRTT,
J, MupplPhys, ) $IK/Volume 7, No. 1/Ref. 2-//j (1944). However, in this case poly! -Composition-〇Temperature during melting is 220℃
Then, a direct current of 3ρOOV is applied, and the value immediately after 9 is taken as the specific resistance at the time of melting.

(4) The b value, which is an index of the yellowness of Bo1 ester, was determined by
o-jD type). The larger the b value, the stronger the yellowish tinge. Count the number of interference fringes/■Convert to the number per 8 and get 9. The reflectance of the user's mirror is 6js, and the reflectance of the mirror is 100 times higher. Trench nine measurement wavelength welfare O1!
Reference μ.

(6) Measuring the coefficient of friction of a film The coefficient of static friction was measured using the method described in A8TM D-/I.

Example: 10 parts of dimethyl terephthalate, 70 parts of ethylene glycol, and 0.10 parts of calcium acetate hydrate were placed in a reactor, heated and heated to remove methanol, and a transesterification reaction was carried out. λ21'C for about 3 hours after the start of the reaction
was reached and the transesterification reaction was comprehensively completed.

Next, 0.21 part of calcium acetate hydrate and 0.1 part of triethyl phosphate were added at the same time, and after 70 minutes, 0.04 part of trimethylphosne was added. (At this time, the ratio between the total amount of phosphorus compounds and the total amount of calcium compounds was 8 J.) After a further 4 cj minutes, antipropylene trioxide (O) and OS part were added as a polycondensation catalyst, and the temperature was started to rise. .

After the addition of trimethyl phosphate, no particles were gradually formed, and when the temperature in the system reached 2°C after 50 minutes from the start of temperature rise, the reaction system was in a good condition with a lot of gas.

Next, -0 parts of magnesium acetate tetrahydrate Q were added at this point. (At this time, the i amount ratio between the total amount of phosphorus compounds and the combination of calcium compounds and magnesium compounds is o, r).Next, a polycondensation reaction was carried out by a conventional method, that is, the temperature was ≠! The temperature is gradually raised from ℃ to finally reach ℃, and the pressure gradually decreases from normal pressure to 0.
Achieved 1wmHg.

After 4IliI, the reaction was stopped and a polyester with an intrinsic viscosity of 0.47 was obtained. When the amount of precipitated particles in the polyester was measured, it was 0. J 1 weight - 9.

In addition, the precipitated particles contain 0% by weight of calcium element and 7.1% by weight of phosphorus element. The element gnesium is substantially free of (7.7% by weight or less) and 9.

The solution haze of the polyester containing the precipitated particles obtained at this time was J? -, the specific resistance when melting is z, rxi□'Ω
-It was.

Next, the obtained nine polyester was extruded into a sheet form from an extruder at 220° C. and an amorphous sheet was formed using an electrostatic cooling method. The conditions for applying static electricity at this time are as follows. That is, using a tungsten wire with a diameter θ, /- as a positive electrode,
This was stretched on the upper surface of the rotating cooling drum in a direction perpendicular to the flow of the sheet, and a DC voltage of 9000 V was applied to it to form a circle.

Obtain an amorphous sheet, 3.0 times in the longitudinal direction, KJ in the lateral force direction,
The extrusion amount and the speed of the rotary cooling body were adjusted to 111111i to obtain a two-wheel stretched film with a thickness of ljμ.
At this time, t, 9 observed the relationship between the rotary cooling body o, ii* and the bound bubbles.

Gradually increase the rotating cooling body speed from 20 m/fi,
II Orn/%, no bound bubbles were generated,
The thickness unevenness of the 92-axis stretched film obtained when the film was 4 was small and was sufficiently satisfactory.
Surface roughness was measured using multiple interference method. 1st order and 0th order
The number of interference fringes is /10 and 71, respectively, in 7 ml.No third-order interference fringes are observed, and the film has an extremely uniform and fine surface structure.The coefficient of static friction of the film is 0.9. J
A friend that is low and has excellent workability.

These results are summarized in #I1 along with the following examples and comparative examples.
Shown in the table.

Comparative example 1~ko! J! In Koji Example/, polyester was obtained in the same manner as in Example 1 except that the conditions shown in Table ls1 were changed, and then a biaxially stretched polyester film was obtained in the same manner as in Example 1 using wrinkled polyester. 90 Comparative Example 7 The 9 film obtained with #1 melting of the raw polyester has precipitated particles consisting of calcium salts of phosphoric acid and tinnitus W/1tlI conductor, and is excellent in terms of film surface shape and slipperiness. It has the inherent disadvantage that it has a high specific resistance and poor electrostatic castability/Ic.

*Example/ is a quantitative determination of i% of precipitated particles produced in Comparative Example 1 (this point was successfully improved by a clever method of adding a Q-r magnesium compound).

On the other hand, in Comparative Example λ, the magnesium compound is added in the same amount as in Example 1, but it is surprising that the addition time is before the formation of precipitated particles and before ripening, for example, at the same time as trimethylphos 7-ide. In particular, this shows that a completely different result from the example/example can be obtained. That is, no formation of the intended precipitated particles was observed in the polyester, and the surface of the film was almost flat.

Therefore, the film has an extremely high coefficient of friction and is therefore undesirable as a film for use in the present invention.

Example 1 In the production of the polyester of Example 1, acetic acid! Gnesicum tetrahydrate a [D,, 20@'s base ge*v Ngan tetrahydrate 0. Ko! A polyester was obtained in the same manner as in Example 1 except that 9 parts were added.

The O resistivity of the polyester osim is j, /X /
0'Ω - There are no precipitated particles in the polyester.
34 weight - I can't meet you.

Note that the wrinkle precipitated particles contain 1.1% calcium element by weight.
Phosphorus element is 7.4 weight - Manganese element of Kanakura Rete Marumono is 0. ! The weight of the bag contains substantially less than the bag.

Next, using cough polyester, an amorphous sheet was obtained by the electrostatic application cooling method under the same conditions as in Example 1. No air bubbles were observed at all.

Next, a biaxially stretched film was obtained in the same manner as in Example 1. The constant thinning of the 90# film is shown in Table 1, and the friction coefficient was sufficiently small and the film had excellent lubricity.

*Example J Instead of using 0.10s of calcium acetate monohydrate as a transesterification agent in the production of polyester in Example J, 0976 parts of lithium acetate dihydrate and o, or parts of calcium acetate hydrate were used. The transesterification reaction was otherwise carried out in the same manner as in Example.

Next, 0.3 parts of triethyl phosphate (k/V times the total amount of calcium and lithium compounds) was added, and o and or parts of antimony trioxide were added to carry out a polycondensation reaction in a conventional manner.

After 20 minutes of starting the polymerization reaction, the temperature reached 270 DEG C. and the pressure reached 3 Hg, and the inside of the reaction system became quite cloudy.

At this point, magnesium acetate tetrahydrate 0. / 1 part (at this time, the equivalent ratio of the phosphorus compound, calcium compound, lithium compound, and magnesium compound combined is 0.1
becomes j. ) was added to continue the polycondensation reaction.

The finally obtained polyester with an intrinsic viscosity of 0.6≠ had a specific resistance when melted of 80×10”Ω−, and the polyester contained o, +−weight− of precipitated particles. .

The wrinkle precipitated particles contain 7.7% by weight and 7.1% by weight of Kaltaf 5 elements, 5 elements Riteku, and phosphorus element, respectively, and the content of the i gnesium element is 0. .1
Next, a multi-thermoformed sheet was obtained by the electrostatic application cooling method under the same conditions as those used in the experiment using the polyester with a weight less than or equal to 9. At this time, a rotary cooling body was used. Even when the speed was increased to 30 m/7 min, no bound bubbles were observed.

Next, a biaxially stretched film was obtained in the same manner as in Example 1.

The measurement results for the cough film were 11eK, and it was rated 4, which had a good feel and was highly slippery.

Comparative Example J - Polynisdel was obtained in exactly the same manner as in Example J, except that in Example J, magnesium acetate tetrahydrate was not added.

The O resistivity of Mukuro polyester when melted is 7. /X10”Ω-
When an amorphous sheet was obtained using the polyester No. 1 by the electrostatic cooling method in the same manner as in Example, bound bubbles were observed when the speed of the rotary cooling body was increased to 7%. Ta.

As is clear from a comparison between Example J and Comparative Example 3, in the case of the present invention, in which a specific amount of magnesium compound is cross-linked after precipitated particles are formed, polyester can be formed without changing the surface morphology of the film. It is possible to lower the specific resistance during melting of l11, and to improve the electrostatic application castability.

Claims (1)

[Scope of Claims] (1) Precipitated particles containing lithium and/or calcium and phosphorus elements are 0, oi to 1, and a magnesium compound soluble in polyester and/or 9 is -f/gan. Polyester composition (2) containing the compound in an amount of 0.0j-1 mol as a metal element based on the total acid components of the polyester.The ratio of the phosphorus element to the total metal elements contained in the polyester is 06! -/The composition according to claim 7 (3) The composition according to claim 1, characterized in that the specific resistance when melted is jX/θ8Ω−υ or less In the method for producing a polyester using the composition described in Section 9@λ, in which chill is used as the acid component and ethylene glycol is used as the glycol component, the reaction system Kl is added before the polycondensation reaction is completed.
Qualitatively dissolved lithium compounds and/or phosphorous compounds are reacted with calcium compounds and phosphorous foods to produce particles containing calcium and phosphorus elements, which are then soluble in the polyester. What! Method for producing polyester (5) characterized by adding a gnesimized food and/or a manganese compound The i amount ratio of the phosphorus element to all the metal elements added to the polyester is 0. (6) The method (6) according to claim 7, characterized in that the amount of the phosphorus compound added is about 100% or more as an element relative to the lithium and/or calcium compound. The method according to claim 1 or claim 1